CA2172959A1 - Process for detecting marked mineral oils and new azo dyes - Google Patents
Process for detecting marked mineral oils and new azo dyesInfo
- Publication number
- CA2172959A1 CA2172959A1 CA002172959A CA2172959A CA2172959A1 CA 2172959 A1 CA2172959 A1 CA 2172959A1 CA 002172959 A CA002172959 A CA 002172959A CA 2172959 A CA2172959 A CA 2172959A CA 2172959 A1 CA2172959 A1 CA 2172959A1
- Authority
- CA
- Canada
- Prior art keywords
- strongly
- hydrogen
- alkyl
- yellow
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000987 azo dye Substances 0.000 title claims abstract description 44
- 239000002480 mineral oil Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 51
- -1 phenylazo Chemical group 0.000 claims abstract description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003550 marker Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims abstract description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 7
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 5
- 150000003868 ammonium compounds Chemical class 0.000 claims description 5
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000012071 phase Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 33
- 239000002283 diesel fuel Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 229940083608 sodium hydroxide Drugs 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 150000001989 diazonium salts Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- ZJLAVECTZKKXEJ-UHFFFAOYSA-N 3-[(benzyldiazenyl)methyl]aniline;hydrochloride Chemical compound Cl.NC1=CC=CC(CN=NCC=2C=CC=CC=2)=C1 ZJLAVECTZKKXEJ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HCSCWJCZRCSQFA-UHFFFAOYSA-N 1-methylpyrrolidin-2-one;hydrate Chemical compound O.CN1CCCC1=O HCSCWJCZRCSQFA-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- XXAGRMCFQRKKEE-UHFFFAOYSA-N 2-(ethylamino)-4-methylphenol Chemical compound CCNC1=CC(C)=CC=C1O XXAGRMCFQRKKEE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 description 2
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 2
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical compound CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000394567 Viola pubescens Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- 150000004350 1,4-dihydroxyanthraquinones Chemical class 0.000 description 1
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- JEQDLQXVZAUQIT-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)diazenyl]-3-phenylphenol Chemical class Oc1ccccc1N=Nc1c(O)cccc1-c1ccccc1 JEQDLQXVZAUQIT-UHFFFAOYSA-N 0.000 description 1
- KTVOLKQQNNIGGM-UHFFFAOYSA-N 2-[[4-[4-[(2-hydroxy-5-nonylphenyl)diazenyl]-3-methylphenyl]-2-methylphenyl]diazenyl]-4-nonylphenol Chemical compound CCCCCCCCCC1=CC(N=NC2=C(C)C=C(C=C2)C2=CC(C)=C(C=C2)N=NC2=CC(CCCCCCCCC)=CC=C2O)=C(O)C=C1 KTVOLKQQNNIGGM-UHFFFAOYSA-N 0.000 description 1
- UANWURKQKKYIGV-UHFFFAOYSA-N 2-methoxypropan-1-amine Chemical compound COC(C)CN UANWURKQKKYIGV-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LFZDEAVRTJKYAF-UHFFFAOYSA-L barium(2+) 2-[(2-hydroxynaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21.C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 LFZDEAVRTJKYAF-UHFFFAOYSA-L 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- ONTQJDKFANPPKK-UHFFFAOYSA-L chembl3185981 Chemical compound [Na+].[Na+].CC1=CC(C)=C(S([O-])(=O)=O)C=C1N=NC1=CC(S([O-])(=O)=O)=C(C=CC=C2)C2=C1O ONTQJDKFANPPKK-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940075911 depen Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005932 isopentyloxycarbonyl group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229940102398 methyl anthranilate Drugs 0.000 description 1
- DJDSLBVSSOQSLW-UHFFFAOYSA-N mono(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(O)=O DJDSLBVSSOQSLW-UHFFFAOYSA-N 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005933 neopentyloxycarbonyl group Chemical group 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005934 tert-pentyloxycarbonyl group Chemical group 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/26—Amino phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
- C09B31/02—Disazo dyes
- C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
- C09B31/062—Phenols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/003—Marking, e.g. coloration by addition of pigments
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/007—Coloured or dyes-containing lubricant compositions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/2882—Markers
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Cosmetics (AREA)
- Lubrication Of Internal Combustion Engines (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
- Developing Agents For Electrophotography (AREA)
- Plural Heterocyclic Compounds (AREA)
- Coloring (AREA)
- Spectrometry And Color Measurement (AREA)
- Paper (AREA)
Abstract
A process for detecting marked mineral oils by treating the marked mineral oil with an extracting agent containing water, a solvent and a base, in which use is made as the marking agent of an azo dye of formula (I), in which ring A may be benzo-anellated and l is 1 or 2, m is 1 to 4, X1 is hydrogen, C1-C4-alkyl, cyano, nitro or possibly substituted phenylazo; X2 is hydrogen, C1-C4-alkyl, cyano, nitro, C1-C4-alkoxy or C1-C16-alkoxy carbonyl; X3 is hydrogen, C1-C4-alkyl, cyano or C1-C16-alkoxy carbonyl and X4 is hydrogen, hydroxy, possibly substituted C1-C8-alkyl, C1-C4-alkoxy, amino, C1-C4-dialkyl amino or possibly substituted C1-C16-monoalkylamino. A partially or completely water-miscible organic solvent is used as the solvent and the base is an alkaline or alkaline earth hydroxide, an alkali carbonate or a quaternary ammonium hydroxide. The invention also relates to the use of azo dyes as marking agents for mineral oils and novel azo dyes.
Description
2112qS9 O.Z. 0050/44380 Detection of marked mineral oils and novel azo dYes The pre~ent invention relates to a novel method for detecting azo dye marked mineral oils, the use of monoazo or di~azo dyes as markers for mineral oils, and novel azo dyes.
US-A-5 156 653 discloses the use of phenylazo-phenols for marking mineral oils. The markers are detec-ted there by 8h~k;~ the marked mineral oil with a mixture of water, diethylene glycol and methoxyethoxy-propylamine to form a mineral oil phase and an aqueousphase cont~; n; ng the azo dye. However, it has been found that the method of detection described there is not satisfactory. It does not ha~e universal utility and frequently produces only an extremely weak coloring of the aqueous phase, since some of the dye used remains in the oil phase.
US-A-3 764 273 describes the extraction of quinizarin derivatives and of specific azo dyes, inter alia with aqueous alkali and dimethyl sulfoxide.
GB-A-905 321, Chemical Abstracts 81 (1974), 51088q and FR-A-2 160 666 disclose azo dyes of the below-cited formula IA. EP-A-12 297, EP-A-31 572, US-A-3 056 642 and above-cited FR-A-2 160 666 describe the use of azo dyes for coloring mineral oils.
It is an object of the present invention to provide a novel method for detecting azo dye marked mineral oils which i8 simple to carry out and by means of which the markers, even in low concentrations, can be visibilized by strong color reaction.
We have ~ound that this object is achieved by a method for detecting azo dye marked mineral oils by treating the marked mineral oil with an extractant comprising water, a solvent and a base, the azo dye transferring from the mineral oil into the aqueous phase, 35 which comprises using as marker an azo dye of the formula Ia AMENDED SHEET
US-A-5 156 653 discloses the use of phenylazo-phenols for marking mineral oils. The markers are detec-ted there by 8h~k;~ the marked mineral oil with a mixture of water, diethylene glycol and methoxyethoxy-propylamine to form a mineral oil phase and an aqueousphase cont~; n; ng the azo dye. However, it has been found that the method of detection described there is not satisfactory. It does not ha~e universal utility and frequently produces only an extremely weak coloring of the aqueous phase, since some of the dye used remains in the oil phase.
US-A-3 764 273 describes the extraction of quinizarin derivatives and of specific azo dyes, inter alia with aqueous alkali and dimethyl sulfoxide.
GB-A-905 321, Chemical Abstracts 81 (1974), 51088q and FR-A-2 160 666 disclose azo dyes of the below-cited formula IA. EP-A-12 297, EP-A-31 572, US-A-3 056 642 and above-cited FR-A-2 160 666 describe the use of azo dyes for coloring mineral oils.
It is an object of the present invention to provide a novel method for detecting azo dye marked mineral oils which i8 simple to carry out and by means of which the markers, even in low concentrations, can be visibilized by strong color reaction.
We have ~ound that this object is achieved by a method for detecting azo dye marked mineral oils by treating the marked mineral oil with an extractant comprising water, a solvent and a base, the azo dye transferring from the mineral oil into the aqueous phase, 35 which comprises using as marker an azo dye of the formula Ia AMENDED SHEET
2 1 72q59 - 2 - O.Z. 0050/44380 x2 HO
Xl ~ N = ~ ~ (Ia), X3 ~ d -( X4 ) m where m iR from 1 to 4, Xl i~ hydrogen, cyano, nitro or phenylazo which may be monosubstituted or disub~tituted by C1-C4-alkyl, X2 is hydrogen, Cl-C4-alkyl, C1-C4-alkoxy or Cl-C13-alkoxycarbonyl, X3 is hydrogen or Cl-C4-alkyl, and X4 i~ hydrogen or Cl-C4-alkyl, which may be phenyl-sub~tituted, or of the formula Ib X1 ~ N = N ~ X4 (Ib) \~:/ \~ Xs X3 x6 where Xl i8 hydrogen, or Cl-C4-alkyl-sub~tituted phenylazo, X2 is hydrogen, X3 i8 hydrogen or Cl-C4-alkyl, X4 is hydrogen, Cl-C4-alkyl, C1-C4-dialkylamino or C1-C16-monoalkylamino, X5 i8 hydrogen or Cl-C4-alkyl, and X6 is hydrogen, Cl-C4-alkyl or C1-C4-alkoxy, with the provi~o that a) at least one of the three radicals Xl, x2 and X3 is different from hydrogen, b) x2 may also be cyano when X4 is C1-C4-dialkylamino, c) x2 may also be Cl-C4-alkoxycarbonyl when all the radicals X4, X5 and x6 are different from hydrogen, and d) one of the AMENDED SHEET
~ 1 7~9S~
Xl ~ N = ~ ~ (Ia), X3 ~ d -( X4 ) m where m iR from 1 to 4, Xl i~ hydrogen, cyano, nitro or phenylazo which may be monosubstituted or disub~tituted by C1-C4-alkyl, X2 is hydrogen, Cl-C4-alkyl, C1-C4-alkoxy or Cl-C13-alkoxycarbonyl, X3 is hydrogen or Cl-C4-alkyl, and X4 i~ hydrogen or Cl-C4-alkyl, which may be phenyl-sub~tituted, or of the formula Ib X1 ~ N = N ~ X4 (Ib) \~:/ \~ Xs X3 x6 where Xl i8 hydrogen, or Cl-C4-alkyl-sub~tituted phenylazo, X2 is hydrogen, X3 i8 hydrogen or Cl-C4-alkyl, X4 is hydrogen, Cl-C4-alkyl, C1-C4-dialkylamino or C1-C16-monoalkylamino, X5 i8 hydrogen or Cl-C4-alkyl, and X6 is hydrogen, Cl-C4-alkyl or C1-C4-alkoxy, with the provi~o that a) at least one of the three radicals Xl, x2 and X3 is different from hydrogen, b) x2 may also be cyano when X4 is C1-C4-dialkylamino, c) x2 may also be Cl-C4-alkoxycarbonyl when all the radicals X4, X5 and x6 are different from hydrogen, and d) one of the AMENDED SHEET
~ 1 7~9S~
- 3 - O.z. 0050~44380 radicals X1, x2 or X3 may also be nitro when X4 is Cl-C16-mo~o~lkylamino and x6 is C1-C4-alkyl, as solvent a partially or completely water-miscible organic solvent, and as base an alkali or alkaline earth metal hydroxide, an alkali metal carbonate or an ammonium compound of the formula II
-- R~
R2- N R4 oH9 (II), _ l3 where R1, R2, R3 and R4 are each independently of the others C1-C16-alkyl or benzyl.
Any alkyl appearing in the abovementioned formula I may be 8 traight-chain or branched.
Unless otherwise stated, substituents in substi-tuted phenyl or naphthyl appearing in the abovementioned formula I need not all be the same.
X2 X3 X4 X5 x6 Rl R2, R3 and R4 are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
X4, R1, R2, R3 and R4 may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
R1, R2, R3 and R4 may each also be for example nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetra-decyl, pentadecyl or hexadecyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the oxo process alcohols - cf. Ull-manns Encyclopadie der technischen Chemie, 4th edition, Volume 7, pages 215 to 217, and Volume 11, pages 435 and 436).
X4 may also be for example dimethylamino, di-ethylamino, dipropylamino, diisopropylamino, dibutyl-AMENDED SHEET
- ~112~59
-- R~
R2- N R4 oH9 (II), _ l3 where R1, R2, R3 and R4 are each independently of the others C1-C16-alkyl or benzyl.
Any alkyl appearing in the abovementioned formula I may be 8 traight-chain or branched.
Unless otherwise stated, substituents in substi-tuted phenyl or naphthyl appearing in the abovementioned formula I need not all be the same.
X2 X3 X4 X5 x6 Rl R2, R3 and R4 are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
X4, R1, R2, R3 and R4 may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
R1, R2, R3 and R4 may each also be for example nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetra-decyl, pentadecyl or hexadecyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial names derived from the oxo process alcohols - cf. Ull-manns Encyclopadie der technischen Chemie, 4th edition, Volume 7, pages 215 to 217, and Volume 11, pages 435 and 436).
X4 may also be for example dimethylamino, di-ethylamino, dipropylamino, diisopropylamino, dibutyl-AMENDED SHEET
- ~112~59
- 4 - 0. Z . 0050/44380 amino, methylamino, ethylamino, propylamino, isopropyl-amino, butylamino, isobutylamino, sec-butylamino, pentyl-amino, isopentyl~;no, neopentylamino, tert-pentylamino, hexylamino, 2-methylpentylamino, heptylamino, octylamino,
5 2-ethylhexylamino, isooctylamino, nonylamino, isononyl-amino, decylamino, isodecylamino, undecylamino, dodecyl-amino, tridecylamino, 3,5,5,7-tetramethylnonylamino, isotridecylamino, tetradecylamino, pentadecylamino, hexadecylamino, benzyl or 1- or 2-phenylethyl.
Xl may also be for example phenylazo, 2-, 3- or 4-methylphenylazo or 2,4 - or 2,6-dimethylphenylazo.
X2, X4 and x6 may each also be for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
X2 may also be for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxy-carbonyl, 2 -methylpentyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isooctyloxy-carbonyl, nonyloxycarbonyl, isononyloxycarbonyl, decyloxycarbonyl, i sodecyloxycarbonyl, undecyloxycar-bonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, i80-tridecyloxycarbonyl, tetradecyloxycarbonyl, penta-decyloxycarbonyl or hexadecyloxycarbonyl.
Very particular preference is given to using in the method of the invention azo dyes of the formula Ia where X4 is hydrogen or 1-phenylethyl.
Very particular preference is further given to using in the method of the invention azo dyes of the formula Ia where X1 is hydrogen or methyl-monosubstituted phenylazo, x2 is methyl or Cl-Cl3-alkoxycarbonyl, and X3 is hydrogen or methyl.
Attention i8 drawn very particularly to a method where the azo dyes used have the formula Ia where Xl is AMENDED SHEET
- ~ 1 12q~
- 5 - O.Z. 0050/44380 methyl-monosubstituted phenylazo, x2 is methyl, and X3 i8 hydrogen or methyl.
Suitable alkali or alkaline earth metal hydroxides or alkali metal carbonates for use in the method of the invention include for example lithium hydroxide, sodium hydroxide, pota~sium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbon-ate, sodium carbonate and potassium carbonate.
Suitable ammonium compounds of the formula II
include for example tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydrox-ide, tetrabutylammonium hydroxide, benzyltrimethyl-ammonium hydroxide, benzyltriethyl~mmonium hydroxide and benzyltributylr ~;um hydroxide.
The use of alkali or alkaline earth metal hydrox-ides as base is preferred with particular attention being drawn to alkali metal hydroxides.
Particular preference is given to the use of lithium hydroxide, sodium hydroxide or potassium hydrox-ide as base, sodium hydroxide being of particular import-ance.
Since the extractant includes water, the alkali or alkaline earth metal hydroxides, alkali metal carbon-ates or ammonium compounds of the formula II are prefer-ably used directly in the form of an aqueous solution,this aqueous solution generally having an alkali or alkaline earth metal hydroxide, alkali metal carbonate or ammonium compound of the formula II content from 0.1 to 10% by weight, preferably from 1 to 10% by weight, each percentage being based on the weight of the aqueous solution.
Suitable solvents are partially or completely water-miscible organic solvents. This i~cludes for example amides, especially carboxamides, such as form-amide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, pyrrolidin-2-AMENDED SHEET
- ~1 7~95~ o.z. 0050/44380 one, 1-methylpyrrolidin-2-one (NMP), 1,3-dimethylhexa-hydropyrimid-2-one or hexamethylphosphonic triamide, N,N,N',N'-tetramethylguanidine, acetonitrile, nitromethane, amines, such as 2-aminoethanol, 1,10-5diamino-4,7-dioxadecane, 1,13-diamino-4,7,10-trioxatridecane, 2- or 3-methoxypropylamine, 1,8-bis(dimethylamino)naphthalene or an amine of the formula H2N CH(CH3)CH2[-0CH(CH3)CH2~2 6-OCH2CH(CH3)_NH2, 1-methylpyrazole, dimethyl sulfoxide (DMS0) or sulfolane.
10Preferred sol~ents are 1-methylpyrazole, pyrro-lidin-2-one, 1-methylpyrrolidin-2-one, dimethyl sulfoxide and sulfolane.
In some cases it can also be of advantage for the extractant to include further admixtures, for example 4-nonylphenol, or for the mineral oil to ha~e 4-nonylphenol added to it prior to the extraction.
Based on the weight of the extractant, the proportion of solvent typically ranges from 50 to 99% by weight, preferably from 90 to 99% by weight.
20To mark mineral oil, the azo dyes of the formula I are used either without a solvent or in the form of solutions. Suitable solvents include preferably aromatic hydrocarbons, such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics commercially available from Shell as Shellsol~ AB. The solubility may be improved in a conventional ~-nn~r by using further co-solvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heY~nol, heptanol, octanol, 2-ethylh~Anol or cycloh~Y~nol, glycols, such as butyl-ethylene glycol or methylpropylene glycol, amines, such as triethylamine, dii~ooctylamine, dicyclohexylamine, aniline, N-methylaniline, N,N-dimethylaniline, toluidine or xylidine, alkanolamines, such a~ 3-(2-methoxyethoxy)-propylamine, o-cresol, m-cresol, p-cresol, ketones, such as diethyl ketone or cycloh~x~no~e, lactams, such as ~-AMENDED SHEET
21 729~
- 7 - O.Z. 0050/44380 butyrolactam, carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t-butylphenol or nonylphenol, esters, such as methyl phthalate, ethyl phthalate, 2-ethylhexyl phthalate, ethyl acetate, butyl acetate or cyclohexyl acetate, amides, such as N,N-dimethylformamide, N,N-diethylacetamide or N-methylpyrro-lidin-2-one, or mixtures thereof. To avoid the resulting solution from becoming too viscous, it is generally advisable to use a concentration of azo dye I from 1 to 50% by weight, preferably from 10 to 50% by weight, each percentage being based on the solution.
In the course of the treatment of the marked mineral oil with the extractant, for example by ~h~; ng, the azo dye of the formula I transfers into the aqueous phase, which takes on a distinctly visible color in the process.
The method of the invention provides a very simple means of detecting mineral oils marked with azo dyes of the formula I. A further advantage of the method of the invention is that it permits the extraction of dyes which have only little acidity.
The present invention further provides for the use of azo dyes of the abovementioned formulae Ia and Ib for marking mineral oils.
Preference for marking mineral oils is given to the use of azo dyes of the formula Ia where X4 is hydro-gen or l-phenylethyl.
Preference for marking mineral oils is further given to the use of azo dyes of the formula Ia where X1 is hydrogen or methyl-monosubstituted phenylazo, x2 is methyl or C1-C13-alkoxycarbonyl, and X3 is hydrogen or methyl.
Particular preference for marking mineral oils is given to the use of azo dyes of the formula Ia where X
is methyl-monosubstituted phenylazo, x2 is methyl, and X3 is hydrogen or methyl.
AMENDED SHEET
~ 1 77~959 - 8 - O.Z. 0050/44380 Particular preference for marking mineral oils is further given to the use of azo dye~ of the formula Ic COOY
~ N = N ~ ~ (Ic), where Y iB C7-Cll-alkyl.
Mi~eral oils for the purposes of the present invention include for example power fuels, such as ga~oline, kerosine or diesel fuel, or oils, such as fuel oil or engine oil.
The azo dyes of the fonmula Ia or Ib are espec-ially suitable for marking mineral oils where a form of identification i8 mandatory, for example for tax reasons.
To keep the costs for this to a minimum, it is desirable to keep the amount of marker used to a ~; n; mum.
Marking for the purposes of the present invention is the addition of the azo dyes of the formula Ia or Ib to mineral oils in such a concentration that, to the human eye, the mineral oils have barely any or no visible color, although the dyes of the formulae Ia and Ib are readily and distinctly visibly detectable by the methods of detection more particularly described herein.
To mark mineral oil, the azo dyes of the formula Ia or Ib, a~ mentioned above, are used either without a solvent or in the form of solutions.
The azo dyes of the formula Ia or Ib to be used according to the invention have the advantage of being suitable, depen~;ng on their concentration, of conferring a clearly visible color on mineral oils and/or for use as marker substances.
The azo dyes of the formula Ia or Ib to be used according to the in~ention permit very simple detection AMENDED S~EET
2 1 7295~
- 9 - O.Z. 0050/44380 of marked mineral oils, even if the marker substances are present only in a concentration of about 10 ppm or less.
The azo dyes of the formula Ia have the application advantage of very good solubility and also excellent dilutability. Moreover, in the detection reaction, they give distinctly more bathochromic hues than the dye~ known from US-A-5 156 653.
The azo dyes of the formula Ib are obt~;n~hle in a conventional manner, for example by diazotizing an aniline of the formula III
~2 xl ~ NH2 ~III), where Xl, x2 and X3 are each as defined above, and coupling the resulting diazonium compound with a phenol of the formula IV
Ho ~ xx~ (IV), x6 where X4, X5 and x6 are each as defined above.
The further azo dye~ of the formula Ia are generally compound~ known per se. They are described for example in US-A-5 156 653 or US-A-4 473 376 or can be obtained by the methods mentioned therein.
The Examples which follow illustrate the inven-tion (parts are by weight).
5 ppm of the dye (F1) of the formula AMENDED SHEET
2 1 729 ''~
- 10 - O.Z. 0050/44380 ~ N=N~ N=N~
were dissolved in commercial diesel fuel.
9 parts of the diesel fuel thus marked red were admixed with 0.5 part of a mixture of 9 parts of NMP and 1 part of 1% strength by weight aqueous lithium hydroxide solution and vigorously shaken. After about 1 min an NMP-water phase with a strong ~iolet color separated off as a bottom layer. The supernatant diesel fuel phase was almost colorless. The coloring of the NMP-water phase was llnch~nged after 24 h at room temperature.
Commercial diesel fuel was admixed with 10 ppm of a dye (F2) of the formula COOCgHl 9 ~ N=N~ OH
9 parts of the diesel fuel thus marked red were admixed with 0.5 part of a mixture of 4 parts of dis-15tilled water, 4 parts of 1,10-diamino-4,7-dioxadecane and 2 parts of 10% strength by weight sodium hydroxide solution and ~igorously shaken. After about 1 min an aqueous phase with a strong red color ~eparated off as bottom layer. The supernatant diesel fuel phase wa~0 almost colorless. The coloring of the aqueous phase was ~ed after 24 h at room temperature.
A blank test carried out on unmarked diesel oil AM~ ED SHEET
~ 1 7~59 - 11 - O.Z. 0050/44380 under similar conditions produced an aqueous phase which was almost colorless.
Performing the reaction under similar conditions with a commercial gasoline ~from Aral) marked with the dye F2 produced the same color effect as was obtAine~ in the case of marked diesel fuel.
A blank test carried out on unmarked gasoline (from Aral) under similar conditions produced an aqueous phase which was almost colorless.
Similar detection results were achieved on diesel fuel marked with the dyes listed below using various reagent solutions likewi~e listed below.
Dyes:
AMENDED SHEET
~1 7~95~
- 12 - O. Z . 0050/44380 OH
E' 3 ~ N=N~
OH
F4 ~N=N~
FS ~N_U ~ N 2- ~ (n = 1- 4) C
H3C C6Hs n COOCgHlg OH
Xl may also be for example phenylazo, 2-, 3- or 4-methylphenylazo or 2,4 - or 2,6-dimethylphenylazo.
X2, X4 and x6 may each also be for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
X2 may also be for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxy-carbonyl, 2 -methylpentyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isooctyloxy-carbonyl, nonyloxycarbonyl, isononyloxycarbonyl, decyloxycarbonyl, i sodecyloxycarbonyl, undecyloxycar-bonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, i80-tridecyloxycarbonyl, tetradecyloxycarbonyl, penta-decyloxycarbonyl or hexadecyloxycarbonyl.
Very particular preference is given to using in the method of the invention azo dyes of the formula Ia where X4 is hydrogen or 1-phenylethyl.
Very particular preference is further given to using in the method of the invention azo dyes of the formula Ia where X1 is hydrogen or methyl-monosubstituted phenylazo, x2 is methyl or Cl-Cl3-alkoxycarbonyl, and X3 is hydrogen or methyl.
Attention i8 drawn very particularly to a method where the azo dyes used have the formula Ia where Xl is AMENDED SHEET
- ~ 1 12q~
- 5 - O.Z. 0050/44380 methyl-monosubstituted phenylazo, x2 is methyl, and X3 i8 hydrogen or methyl.
Suitable alkali or alkaline earth metal hydroxides or alkali metal carbonates for use in the method of the invention include for example lithium hydroxide, sodium hydroxide, pota~sium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbon-ate, sodium carbonate and potassium carbonate.
Suitable ammonium compounds of the formula II
include for example tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydrox-ide, tetrabutylammonium hydroxide, benzyltrimethyl-ammonium hydroxide, benzyltriethyl~mmonium hydroxide and benzyltributylr ~;um hydroxide.
The use of alkali or alkaline earth metal hydrox-ides as base is preferred with particular attention being drawn to alkali metal hydroxides.
Particular preference is given to the use of lithium hydroxide, sodium hydroxide or potassium hydrox-ide as base, sodium hydroxide being of particular import-ance.
Since the extractant includes water, the alkali or alkaline earth metal hydroxides, alkali metal carbon-ates or ammonium compounds of the formula II are prefer-ably used directly in the form of an aqueous solution,this aqueous solution generally having an alkali or alkaline earth metal hydroxide, alkali metal carbonate or ammonium compound of the formula II content from 0.1 to 10% by weight, preferably from 1 to 10% by weight, each percentage being based on the weight of the aqueous solution.
Suitable solvents are partially or completely water-miscible organic solvents. This i~cludes for example amides, especially carboxamides, such as form-amide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, pyrrolidin-2-AMENDED SHEET
- ~1 7~95~ o.z. 0050/44380 one, 1-methylpyrrolidin-2-one (NMP), 1,3-dimethylhexa-hydropyrimid-2-one or hexamethylphosphonic triamide, N,N,N',N'-tetramethylguanidine, acetonitrile, nitromethane, amines, such as 2-aminoethanol, 1,10-5diamino-4,7-dioxadecane, 1,13-diamino-4,7,10-trioxatridecane, 2- or 3-methoxypropylamine, 1,8-bis(dimethylamino)naphthalene or an amine of the formula H2N CH(CH3)CH2[-0CH(CH3)CH2~2 6-OCH2CH(CH3)_NH2, 1-methylpyrazole, dimethyl sulfoxide (DMS0) or sulfolane.
10Preferred sol~ents are 1-methylpyrazole, pyrro-lidin-2-one, 1-methylpyrrolidin-2-one, dimethyl sulfoxide and sulfolane.
In some cases it can also be of advantage for the extractant to include further admixtures, for example 4-nonylphenol, or for the mineral oil to ha~e 4-nonylphenol added to it prior to the extraction.
Based on the weight of the extractant, the proportion of solvent typically ranges from 50 to 99% by weight, preferably from 90 to 99% by weight.
20To mark mineral oil, the azo dyes of the formula I are used either without a solvent or in the form of solutions. Suitable solvents include preferably aromatic hydrocarbons, such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aromatics commercially available from Shell as Shellsol~ AB. The solubility may be improved in a conventional ~-nn~r by using further co-solvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heY~nol, heptanol, octanol, 2-ethylh~Anol or cycloh~Y~nol, glycols, such as butyl-ethylene glycol or methylpropylene glycol, amines, such as triethylamine, dii~ooctylamine, dicyclohexylamine, aniline, N-methylaniline, N,N-dimethylaniline, toluidine or xylidine, alkanolamines, such a~ 3-(2-methoxyethoxy)-propylamine, o-cresol, m-cresol, p-cresol, ketones, such as diethyl ketone or cycloh~x~no~e, lactams, such as ~-AMENDED SHEET
21 729~
- 7 - O.Z. 0050/44380 butyrolactam, carbonates, such as ethylene carbonate or propylene carbonate, phenols, such as t-butylphenol or nonylphenol, esters, such as methyl phthalate, ethyl phthalate, 2-ethylhexyl phthalate, ethyl acetate, butyl acetate or cyclohexyl acetate, amides, such as N,N-dimethylformamide, N,N-diethylacetamide or N-methylpyrro-lidin-2-one, or mixtures thereof. To avoid the resulting solution from becoming too viscous, it is generally advisable to use a concentration of azo dye I from 1 to 50% by weight, preferably from 10 to 50% by weight, each percentage being based on the solution.
In the course of the treatment of the marked mineral oil with the extractant, for example by ~h~; ng, the azo dye of the formula I transfers into the aqueous phase, which takes on a distinctly visible color in the process.
The method of the invention provides a very simple means of detecting mineral oils marked with azo dyes of the formula I. A further advantage of the method of the invention is that it permits the extraction of dyes which have only little acidity.
The present invention further provides for the use of azo dyes of the abovementioned formulae Ia and Ib for marking mineral oils.
Preference for marking mineral oils is given to the use of azo dyes of the formula Ia where X4 is hydro-gen or l-phenylethyl.
Preference for marking mineral oils is further given to the use of azo dyes of the formula Ia where X1 is hydrogen or methyl-monosubstituted phenylazo, x2 is methyl or C1-C13-alkoxycarbonyl, and X3 is hydrogen or methyl.
Particular preference for marking mineral oils is given to the use of azo dyes of the formula Ia where X
is methyl-monosubstituted phenylazo, x2 is methyl, and X3 is hydrogen or methyl.
AMENDED SHEET
~ 1 77~959 - 8 - O.Z. 0050/44380 Particular preference for marking mineral oils is further given to the use of azo dye~ of the formula Ic COOY
~ N = N ~ ~ (Ic), where Y iB C7-Cll-alkyl.
Mi~eral oils for the purposes of the present invention include for example power fuels, such as ga~oline, kerosine or diesel fuel, or oils, such as fuel oil or engine oil.
The azo dyes of the fonmula Ia or Ib are espec-ially suitable for marking mineral oils where a form of identification i8 mandatory, for example for tax reasons.
To keep the costs for this to a minimum, it is desirable to keep the amount of marker used to a ~; n; mum.
Marking for the purposes of the present invention is the addition of the azo dyes of the formula Ia or Ib to mineral oils in such a concentration that, to the human eye, the mineral oils have barely any or no visible color, although the dyes of the formulae Ia and Ib are readily and distinctly visibly detectable by the methods of detection more particularly described herein.
To mark mineral oil, the azo dyes of the formula Ia or Ib, a~ mentioned above, are used either without a solvent or in the form of solutions.
The azo dyes of the formula Ia or Ib to be used according to the invention have the advantage of being suitable, depen~;ng on their concentration, of conferring a clearly visible color on mineral oils and/or for use as marker substances.
The azo dyes of the formula Ia or Ib to be used according to the in~ention permit very simple detection AMENDED S~EET
2 1 7295~
- 9 - O.Z. 0050/44380 of marked mineral oils, even if the marker substances are present only in a concentration of about 10 ppm or less.
The azo dyes of the formula Ia have the application advantage of very good solubility and also excellent dilutability. Moreover, in the detection reaction, they give distinctly more bathochromic hues than the dye~ known from US-A-5 156 653.
The azo dyes of the formula Ib are obt~;n~hle in a conventional manner, for example by diazotizing an aniline of the formula III
~2 xl ~ NH2 ~III), where Xl, x2 and X3 are each as defined above, and coupling the resulting diazonium compound with a phenol of the formula IV
Ho ~ xx~ (IV), x6 where X4, X5 and x6 are each as defined above.
The further azo dye~ of the formula Ia are generally compound~ known per se. They are described for example in US-A-5 156 653 or US-A-4 473 376 or can be obtained by the methods mentioned therein.
The Examples which follow illustrate the inven-tion (parts are by weight).
5 ppm of the dye (F1) of the formula AMENDED SHEET
2 1 729 ''~
- 10 - O.Z. 0050/44380 ~ N=N~ N=N~
were dissolved in commercial diesel fuel.
9 parts of the diesel fuel thus marked red were admixed with 0.5 part of a mixture of 9 parts of NMP and 1 part of 1% strength by weight aqueous lithium hydroxide solution and vigorously shaken. After about 1 min an NMP-water phase with a strong ~iolet color separated off as a bottom layer. The supernatant diesel fuel phase was almost colorless. The coloring of the NMP-water phase was llnch~nged after 24 h at room temperature.
Commercial diesel fuel was admixed with 10 ppm of a dye (F2) of the formula COOCgHl 9 ~ N=N~ OH
9 parts of the diesel fuel thus marked red were admixed with 0.5 part of a mixture of 4 parts of dis-15tilled water, 4 parts of 1,10-diamino-4,7-dioxadecane and 2 parts of 10% strength by weight sodium hydroxide solution and ~igorously shaken. After about 1 min an aqueous phase with a strong red color ~eparated off as bottom layer. The supernatant diesel fuel phase wa~0 almost colorless. The coloring of the aqueous phase was ~ed after 24 h at room temperature.
A blank test carried out on unmarked diesel oil AM~ ED SHEET
~ 1 7~59 - 11 - O.Z. 0050/44380 under similar conditions produced an aqueous phase which was almost colorless.
Performing the reaction under similar conditions with a commercial gasoline ~from Aral) marked with the dye F2 produced the same color effect as was obtAine~ in the case of marked diesel fuel.
A blank test carried out on unmarked gasoline (from Aral) under similar conditions produced an aqueous phase which was almost colorless.
Similar detection results were achieved on diesel fuel marked with the dyes listed below using various reagent solutions likewi~e listed below.
Dyes:
AMENDED SHEET
~1 7~95~
- 12 - O. Z . 0050/44380 OH
E' 3 ~ N=N~
OH
F4 ~N=N~
FS ~N_U ~ N 2- ~ (n = 1- 4) C
H3C C6Hs n COOCgHlg OH
6 ~N--~ 8 AMENDED S}IEET
21 7~95q - 13 - O.Z. 0050/44380 COO--1--C~Hl 7 OH
F7~N=N~
COO--i--C8H~ 7 F8~N N~ OH
CH3 c~3 F9~N N~ N N~ OH
AMENDED SHEET
- 2 1 72~59 - 14 - O . Z . 0050/44380 coo-i-c9Hl g ~ OH
Fl 0 ~.3N N~
Fl 1 ~N=N~ OH
E'12 ~N N~ N~OH
AMENDED SHEET
2 1 7 ~ i 5 9 - 1~ - O.Z. 0050/44380 CEi CE~3 Fl 3 ~N=N ~N= N~ OCH ;
OH
Fl 9 02N~ ;~C
C~ CH3 O\ N~C2H5 F15 ~N_N ~ N~
F16 ~N--N ~N= N~OH
N ( C2H5 ) 2 Reagent solutions:
R1 9 parts of NMP and 1 part of 1% strength by weight aqueous lithium hydroxide solution R2 9 part~ of 2-pyrrolidinone and 1 part of 1% ~trength by weight aqueous lithium hydroxide solution R3 9 parts of DMS0 and 1 part of 2% strength by weight aqueous lithium hydroxide solution R4 9.5 parts of 1-methylimidazole and 0.5 part of 5%
strength by weight aqueous lithium hydroxide solu-tion R5 9.5 parts of amine of formula AMENDED SHEET
~1 7~5~
- 16 - O.Z. 0050/44380 H2N-CH(CH3)CH2 ~-OCH(CH3)CH2]2.6-0CH2CH(CH3) NH2 and 0.5 part of 1% strength by weight aqueous lithium hydroxide solution R6 9 parts of 1,3-dimethylhexahydropyrimid-2-one and 1 part of 1% strength by weight aqueous lithium hydroxide solution R7 9 parts of 1,13-diamino-4,7,10-trioxatridecane and 1 part of 1% strength by weight aqueous lithium hydroxide solution R8 5 parts of 3-methoxypropylamine and 1 part of 5%
strength by weight aqueous potassium hydroxide solution R9 4 parts of distilled water, 4 parts of 1,10-diamino-4,7-dioYA~ec~ne and 2 parts of 10% strength by weight sodium hydroxide solution R10 9 parts of DMS0, 1 part of 2% strength by weight aqueous lithium hydroxide solution and 1 part of 4-nonylphenol The following results were obtained:
Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~k; ng ~h~k; ng in diesel fuel 5 3 F1 R2 strongly almost strongly 5 ppm violet colorless red 4 F1 R3 strongly almost strongly 5 ppm reddish colorless red violet 30 5 F1 R4 strongly weakly strongly 5 ppm yellowish red red green 6 F1 R5 strongly weakly strongly 5 ppm red red red 5 7 F1 R6 strongly almost strongly 5 ppm violet colorless red AMENDED SHEET
q - 17 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration RhAk; ng RhAk; ng in diesel fuel 8 F1 R7 strongly colorless strongly 5 ppm violet red 9 F1 R8 yellowish weakly strongly5 ppm brown red red 1010 F1 R9 yellow red strongly5 ppm red 11 F1 R10 strongly weakly strongly 5 ppm dark red red red 12 F2 R1 strongly colorless strongly 10 ppm red yellow 13 F2 R2 strongly colorless strongly 10 ppm red yellow 14 F2 R3 strongly colorless strongly 10 ppm red yellow 2015 F2 R4 strongly colorless strongly 10 ppm red yellow 16 F2 R8 weakly weakly strongly 10 ppm red yellow yellow 17 F2 R10 strongly almost strongly 10 ppm redcolorless yellow 18 F3 R1 strongly colorless strongly 5 ppm orange orange 19 F3 R2 strongly colorless strongly 5 ppm orangeorange 3020 F3 R3 strongly almost strongly 5 ppm orange colorless orange 21 F3 R4 yellowish weakly strongly 5 ppm orange yellow orange 22 F3 R5 strongly colorless strongly 5 ppm orange orange 23 F3 R6 ~trongly slightly strongly 5 ppm orange yellow orange AMENDED SHEET
2 1 7 ~
- 18 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration 8hAk; ng RhAk; ng in diesel fuel 24 F3 R7 strongly colorless strongly 5 ppm orange orange 25 F3 R8 strongly almost strongly 5 ppm orange colorless orange 26 F3 R9 orange slightly strongly 5 ppm yellow orange 27 F3 R10 strongly almost strongly 5 ppm orange colorless orange 28 F4 R1 strongly almost strongly 5 ppm orange colorless orange 29 F4 R2 strongly colorless strongly 5 ppm orange orange 30 F4 R3 strongly almost strongly 5 ppm orange colorless orange 31 F4 R4 strongly weakly strongly 5 ppm orange orange orange 32 F4 R5 strongly colorless strongly 5 ppm orange orange 33 F4 R6 strongly almost strongly 5 ppm orange colorless orange 34 F4 R7 strongly colorless strongly 5 ppm orange orange 35 F4 R8 orange weakly strongly 5 ppm orange orange 36 F4 R9 strongly weakly strongly 5 ppm orange orange orange 37 F4 R10 strongly almost strongly 5 ppm orange colorless orange 38 F5 R1 strongly slightly strongly 20 ppm brownish red red 39 F5 R2 strongly slightly strongly 20 ppm brownish red red AMENDED SHEET
g - 19 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration 8h~k; n~ 8h~k; n~ in diesel fuel 40 F5 R3 strongly almost strongly 20 ppm yellowish colorless red brown 41 F5 R4 strongly red strongly 20 ppm yellowish red brown 42 F5 R5 strongly colorless strongly 20 ppm reddish red brown 43 F5 R6 strongly almost strongly 20 ppm reddish colorless red brown 44 F5 R7 strongly weakly strongly 20 ppm reddish red red brown 45 F5 R8 weakly weakly strongly 20 ppm yellow red red 46 F5 R9 yellow red strongly 20 ppm red 47 F5 R10 strongly weakly strongly 20 ppm light red red brown 48 F6 R1 strongly colorless strongly 10 ppm red yellow 49 F6 R2 strongly colorless strongly 10 ppm red yellow 50 F6 R3 strongly almost strongly lO ppm red colorless yellow 51 F6 R8 yellow weakly strongly 10 ppm yellow yellow 52 F6 R9 weakly weakly strongly lO ppm yellow yellow yellow 53 F6 R10 strongly weakly strongly 10 ppm yellow yellow yellow AMENDED SHEET
21 7~9 - 20 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent a~ueous oily phase oily phase concen-phase after before tration 8~k; ng ~ki ng in diesel fuel 54 F7 R1 strongly slightly strongly 10 ppm orange yellow yellow 55 F7 R2 strongly slightly strongly 10 ppm orange yellow yellow 56 F7 R3 strongly almost strongly 10 ppm orange colorless yellow 57 F7 R8 yellow weakly strongly 10 ppm yellow yellow 58 F7 R9 weakly weakly strongly 10 ppm yellow yellow yellow 59 F7 R10 strongly weakly strongly 10 ppm orange orange yellow 60 F8 R1 strongly colorless strongly 10 ppm orange yellow 61 F8 R2 strongly colorless strongly 10 ppm orange yellow 62 F8 R3 strongly almost strongly 10 ppm orange colorless yellow 63 F8 R8 strongly almost strongly 10 ppm red colorless yellow 64 F8 R9 strongly weakly strongly 10 ppm red yellow yellow 65 F8 R10 strongly almost strongly10 ppm red colorless yellow 66 F9 R1 strongly slightly strongly5 ppm red yellow yellow 67 F9 R2 strongly almost strongly 5 ppm red colorless yellow 68 F9 R3 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 69 F9 R8 strongly almost strongly 5 ppm red colorless yellow AMENDED SHEET
~1 72959 - 2~ - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration shaking ~h~k;ng in diesel fuel 70 F9 R9 strongly weakly strongly 5 ppm red yellow yellow 71 F9 R10 strongly almost strongly 5 ppm red colorless yellow 72 F10 Rl strongly almost strongly 20 ppm orange colorless yellow 73 F10 R2 strongly almo~t strongly 20 ppm orange colorless yellow 74 F10 R3 strongly almost strongly 20 ppm orange colorless yellow 75 F10 R8 strongly weakly strongly 20 ppm orange yellow yellow 76 F10 R9 weakly weakly B trongly 20 ppm yellow yellow yellow 77 F10 R10 strongly slightly strongly 20 ppm orange yellow yellow 78 Fll R1 orange weakly yellow 5 ppm yellow 79 Fll R2 strongly weakly strongly 5 ppm orange orange yellow 80 Fll R3 strongly almost strongly 5 ppm orange colorless yellow 81 Fll R4 strongly almost strongly 5 ppm red colorless yellow 30 82 Fll R5 strongly weakly strongly 5 ppm orange orange yellow 83 Fll R6 strongly weakly strongly 5 ppm orange orange yellow 84 Fll R7 strongly weakly strongly 5 ppm orange orange yellow 85 Fll R8 orange weakly strongly 5 ppm orange yellow AMENDED SHEET
21 1~9~9 - 22 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~k;ng shaking in diesel fuel 86 F11 R9 strongly weakly strongly 10 ppm bright yellow yellow red 87 F11 R10 strongly weakly strongly 10 ppm red yellow yellow 88 F12 R1 strongly almost strongly 5 ppm violet colorless yellow 89 F12 R2 strongly almost strongly 5 ppm violet colorless yellow 1590 F12 R3 strongly almost strongly 5 ppm dark blue colorless yellow 91 F12 R4 strongly weakly strongly 5 ppm green green yellow 92 F12 R5 strongly weakly strongly 5 ppm violet red yellow 93 F12 R6 strongly almost strongly 5 ppm violet colorless yellow 94 F12 R7 strongly almost strongly 5 ppm bluish colorless yellow gray 95 F12 R8 strongly almost strongly 5 ppm reddish colorless yellow violet 96 F12 R9 strongly weakly strongly 5 ppm red yellow yellow 97 F12 RlO strongly almost strongly 5 ppm violet colorless yellow 98 F13 Rl strongly almost strongly 5 ppm violet colorless yellow 3599 F13 R2 strongly weakly strongly 5 ppm yellowish yellow yellow orange 100 F13 R3 strongly almost strongly 5 ppm violet colorless yellow AMENDED SHEET
2~ 7~q~'9 - 23 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration BhA~;ng ~hAk;ng in diesel fuel 101 F13 R4 strongly weakly strongly 5 ppm orange yellow yellow 102 F13 R5 strongly weakly strongly 5 ppm orange yellow yellow 103 F13 R6 strongly weakly strongly 5 ppm orange yellow yellow 104 F13 R7 strongly weakly strongly 5 ppm orange yellow yellow 105 F13 R8 strongly weakly strongly 5 ppm orange yellow yellow 106 F13 R9 strongly weakly strongly 5 ppm red yellow yellow 107 F13 R10 strongly weakly strongly 5 ppm dark red yellow yellow 108 Fl4 R1 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 109 F14 R2 strongly almost strongly 5 ppm violet colorless yellow 110 F14 R3 strongly almost strongly 5 ppm ~iolet colorless yellow 111 Fl4 R4 strongly almost strongly 5 ppm green colorless yellow 112 F14 R5 strongly almost strongly 5 ppm reddish colorless yellow violet 113 F14 R6 strongly almost strongly 5 ppm dark blue colorless yellow 114 F14 R7 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 115 F14 R8 strongly almost strongly 5 ppm bright colorless yellow blue AMENDED SHEET
2 j /' ~ !9 ~ 9 - 24 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~king R~k;n~ in diesel fuel 116 F14 R9 strongly weakly Rtrongly 5 ppm bright yellow yellow blue 117 F14 R10 ~trongly weakly strongly 5 ppm violet yellow yellow 118 F15 R1 strongly weakly strongly 5 ppm yellowish yellow orange brown 119 F15 R2 strongly weakly strongly 5 ppm reddish yellow orange brown 120 F15 R3 strongly weakly strongly 5 ppm reddish yellow orange violet 121 F15 R4 strongly weakly strongly 5 ppm yellow yellow orange 122 F15 R5 strongly weakly strongly 5 ppm red yellow orange 123 F15 R6 strongly weakly strongly 5 ppm yellowish yellow orange green 124 F15 R7 yellowish weakly strongly 5 ppm brown yellow orange 125 F15 R8 greenish weakly strongly 5 ppm gray yellow orange 126 F15 R9 colorles~ weakly strongly 5 ppm yellowish orange orange 127 F15 R10 strongly weakly strongly 5 ppm reddish yellow orange brown 128 F16 R1 strongly weakly strongly 5 ppm orange yellow yellow 129 F16 R2 strongly weakly strongly 5 ppm orange yellow yellow AMENDED SHEET
;~ 7f~95'?
- 25 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~k~ n~ shaking in diesel fuel 130 F16 R3 strongly weakly strongly 5 ppm orange yellow yellow 131 F16 R4 strongly weakly strongly 5 ppm yellow yellow yellow 132 F16 R5 strongly weakly strongly 5 ppm orange yellow yellow 133 F16 R6 strongly weakly strongly 5 ppm orange yellow yellow 134 F16 R7 strongly weakly strongly 5 ppm orange yellow yellow 135 F16 R8 strongly weakly strongly 5 ppm orange yellow yellow 136 F16 R9 strongly weakly strongly 5 ppm orange yellow yellow 137 F16 R10 strongly weakly strongly 5 ppm orange yellow yellow EXAMPLE 138 (Preparation of F9) a) 42.6 g (0.04 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 32 ml of water and 12 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 20 g of ice, 7 ml of toluene and 12 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 3.76 g (0.04 mol) of phenol and 100 ml of water were adjusted with 50% strength by weight sodium hydrox-ide solution to pH 6.4 and admixed at 0C with the diazonium salt solution described under a). The pH
was held between 4 and 5 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH was reduced to 1.5 with 10% strength by AMENDED SHEET
- 26 - O.Z. 0050/44380 weight hydrochloric acid and the precipitated solid was isolated.
Yield: 10.1 g EXANPLE 139 (Preparation of Fll) a) 3.0 g (0.02 mol) of methyl anthranilate were dis-solved at 0C in 30 ml of water, 50 g of ice and 5 ml of concentrated hydrochloric acid and then admixed with 6 ml of 23% strength by weight aqueous sodium nitrite solution. The mixture was then stirred at from 0 to 5C for 30 minutes until a clear solution had formed.
b) 2.7 g (0.02 mol) of 2,3,6-trimethylphenol in 100 ml of water were adjusted with 50% strength by weight sodium hydroxide solution to pH 13 and admixed with the diazonium salt solution described under a).
After stirring overnight the pH was reduced to 2.1 with 10% strength by weight hydrochloric acid and the precipitated solid was isolated.
Yield: 5.8 g EXAMPLE 140 (Preparation of F14) a) 7.19 g (0.05 mol) of p-nitroaniline and 0.1 g of a wetting agent were suspended in 45 ml of water and 17.5 ml of 30% strength by weight hydrochloric acid.
The suspension was then a~;Ye~ with 55 g of ice and 16.5 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 0 to 5C for 1 h.
b) 7.56 g (0.05 mol) of 2-monoethylamino-4-methylphenol were added to 100 ml of water and adjusted with 50%
strength by weight sodium hydroxide solution to pH
10. Then the diazonium salt solution described under a) was added at 5C. The pH was held between 7 and 8 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH dropped to 4.6 and the precipitated solid was filtered off with suction.
~1~ NV~V SHEET
q~
- 27 - O.Z. 0050/44380 Yield: 14.1 g EXAMPLE 141 (Preparation of F15) a) 53.3 g (0.05 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 40 ml of water and 15 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 25 g of ice, 8.4 ml of toluene and 15 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 7.56 g (0.05 mol) of 2-monoethylamino-4-methylphenol were added to 100 ml of water and pH 10 was set with 50% strength by weight sodium hydroxide solution.
Then the diazonium salt solution described under a) was added at 5C. The pH was held between 7 and 8 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH was adjus-ted with hydrochloric acid to 1.5 and the precip-itated solid was filtered off with suction.
Yield: 15.9 g EXANPLE 142 (Preparation of F16) a) 42.6 g (0.04 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 32 ml of water and 12 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 20 g of ice, 7 ml of toluene and 12 ml of 23% strength by weight a~ueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 6.7 g (0.04 mol) of m-N,N-diethylaminophenol were added to 100 ml of water and pH 13.2 was set with 50% strength by weight sodium hydroxide solution.
Then the diazonium salt solution described under a) was added at 5C. The pH was held between 4 and 5 with 10% strength by weight sodium hydroxide 801-ution. After stirring overnight the pH was reduced AMENDED SHEET
- ~8 - O.Z. 0050/44380 to 1.5 with 10% ~trength by weight hydrochloric acid and the precipitated solid was isolated.
Yield: 16 g The same method gives the dyes F12 and F13.
AMENDED SHEET
21 7~95q - 13 - O.Z. 0050/44380 COO--1--C~Hl 7 OH
F7~N=N~
COO--i--C8H~ 7 F8~N N~ OH
CH3 c~3 F9~N N~ N N~ OH
AMENDED SHEET
- 2 1 72~59 - 14 - O . Z . 0050/44380 coo-i-c9Hl g ~ OH
Fl 0 ~.3N N~
Fl 1 ~N=N~ OH
E'12 ~N N~ N~OH
AMENDED SHEET
2 1 7 ~ i 5 9 - 1~ - O.Z. 0050/44380 CEi CE~3 Fl 3 ~N=N ~N= N~ OCH ;
OH
Fl 9 02N~ ;~C
C~ CH3 O\ N~C2H5 F15 ~N_N ~ N~
F16 ~N--N ~N= N~OH
N ( C2H5 ) 2 Reagent solutions:
R1 9 parts of NMP and 1 part of 1% strength by weight aqueous lithium hydroxide solution R2 9 part~ of 2-pyrrolidinone and 1 part of 1% ~trength by weight aqueous lithium hydroxide solution R3 9 parts of DMS0 and 1 part of 2% strength by weight aqueous lithium hydroxide solution R4 9.5 parts of 1-methylimidazole and 0.5 part of 5%
strength by weight aqueous lithium hydroxide solu-tion R5 9.5 parts of amine of formula AMENDED SHEET
~1 7~5~
- 16 - O.Z. 0050/44380 H2N-CH(CH3)CH2 ~-OCH(CH3)CH2]2.6-0CH2CH(CH3) NH2 and 0.5 part of 1% strength by weight aqueous lithium hydroxide solution R6 9 parts of 1,3-dimethylhexahydropyrimid-2-one and 1 part of 1% strength by weight aqueous lithium hydroxide solution R7 9 parts of 1,13-diamino-4,7,10-trioxatridecane and 1 part of 1% strength by weight aqueous lithium hydroxide solution R8 5 parts of 3-methoxypropylamine and 1 part of 5%
strength by weight aqueous potassium hydroxide solution R9 4 parts of distilled water, 4 parts of 1,10-diamino-4,7-dioYA~ec~ne and 2 parts of 10% strength by weight sodium hydroxide solution R10 9 parts of DMS0, 1 part of 2% strength by weight aqueous lithium hydroxide solution and 1 part of 4-nonylphenol The following results were obtained:
Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~k; ng ~h~k; ng in diesel fuel 5 3 F1 R2 strongly almost strongly 5 ppm violet colorless red 4 F1 R3 strongly almost strongly 5 ppm reddish colorless red violet 30 5 F1 R4 strongly weakly strongly 5 ppm yellowish red red green 6 F1 R5 strongly weakly strongly 5 ppm red red red 5 7 F1 R6 strongly almost strongly 5 ppm violet colorless red AMENDED SHEET
q - 17 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration RhAk; ng RhAk; ng in diesel fuel 8 F1 R7 strongly colorless strongly 5 ppm violet red 9 F1 R8 yellowish weakly strongly5 ppm brown red red 1010 F1 R9 yellow red strongly5 ppm red 11 F1 R10 strongly weakly strongly 5 ppm dark red red red 12 F2 R1 strongly colorless strongly 10 ppm red yellow 13 F2 R2 strongly colorless strongly 10 ppm red yellow 14 F2 R3 strongly colorless strongly 10 ppm red yellow 2015 F2 R4 strongly colorless strongly 10 ppm red yellow 16 F2 R8 weakly weakly strongly 10 ppm red yellow yellow 17 F2 R10 strongly almost strongly 10 ppm redcolorless yellow 18 F3 R1 strongly colorless strongly 5 ppm orange orange 19 F3 R2 strongly colorless strongly 5 ppm orangeorange 3020 F3 R3 strongly almost strongly 5 ppm orange colorless orange 21 F3 R4 yellowish weakly strongly 5 ppm orange yellow orange 22 F3 R5 strongly colorless strongly 5 ppm orange orange 23 F3 R6 ~trongly slightly strongly 5 ppm orange yellow orange AMENDED SHEET
2 1 7 ~
- 18 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration 8hAk; ng RhAk; ng in diesel fuel 24 F3 R7 strongly colorless strongly 5 ppm orange orange 25 F3 R8 strongly almost strongly 5 ppm orange colorless orange 26 F3 R9 orange slightly strongly 5 ppm yellow orange 27 F3 R10 strongly almost strongly 5 ppm orange colorless orange 28 F4 R1 strongly almost strongly 5 ppm orange colorless orange 29 F4 R2 strongly colorless strongly 5 ppm orange orange 30 F4 R3 strongly almost strongly 5 ppm orange colorless orange 31 F4 R4 strongly weakly strongly 5 ppm orange orange orange 32 F4 R5 strongly colorless strongly 5 ppm orange orange 33 F4 R6 strongly almost strongly 5 ppm orange colorless orange 34 F4 R7 strongly colorless strongly 5 ppm orange orange 35 F4 R8 orange weakly strongly 5 ppm orange orange 36 F4 R9 strongly weakly strongly 5 ppm orange orange orange 37 F4 R10 strongly almost strongly 5 ppm orange colorless orange 38 F5 R1 strongly slightly strongly 20 ppm brownish red red 39 F5 R2 strongly slightly strongly 20 ppm brownish red red AMENDED SHEET
g - 19 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration 8h~k; n~ 8h~k; n~ in diesel fuel 40 F5 R3 strongly almost strongly 20 ppm yellowish colorless red brown 41 F5 R4 strongly red strongly 20 ppm yellowish red brown 42 F5 R5 strongly colorless strongly 20 ppm reddish red brown 43 F5 R6 strongly almost strongly 20 ppm reddish colorless red brown 44 F5 R7 strongly weakly strongly 20 ppm reddish red red brown 45 F5 R8 weakly weakly strongly 20 ppm yellow red red 46 F5 R9 yellow red strongly 20 ppm red 47 F5 R10 strongly weakly strongly 20 ppm light red red brown 48 F6 R1 strongly colorless strongly 10 ppm red yellow 49 F6 R2 strongly colorless strongly 10 ppm red yellow 50 F6 R3 strongly almost strongly lO ppm red colorless yellow 51 F6 R8 yellow weakly strongly 10 ppm yellow yellow 52 F6 R9 weakly weakly strongly lO ppm yellow yellow yellow 53 F6 R10 strongly weakly strongly 10 ppm yellow yellow yellow AMENDED SHEET
21 7~9 - 20 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent a~ueous oily phase oily phase concen-phase after before tration 8~k; ng ~ki ng in diesel fuel 54 F7 R1 strongly slightly strongly 10 ppm orange yellow yellow 55 F7 R2 strongly slightly strongly 10 ppm orange yellow yellow 56 F7 R3 strongly almost strongly 10 ppm orange colorless yellow 57 F7 R8 yellow weakly strongly 10 ppm yellow yellow 58 F7 R9 weakly weakly strongly 10 ppm yellow yellow yellow 59 F7 R10 strongly weakly strongly 10 ppm orange orange yellow 60 F8 R1 strongly colorless strongly 10 ppm orange yellow 61 F8 R2 strongly colorless strongly 10 ppm orange yellow 62 F8 R3 strongly almost strongly 10 ppm orange colorless yellow 63 F8 R8 strongly almost strongly 10 ppm red colorless yellow 64 F8 R9 strongly weakly strongly 10 ppm red yellow yellow 65 F8 R10 strongly almost strongly10 ppm red colorless yellow 66 F9 R1 strongly slightly strongly5 ppm red yellow yellow 67 F9 R2 strongly almost strongly 5 ppm red colorless yellow 68 F9 R3 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 69 F9 R8 strongly almost strongly 5 ppm red colorless yellow AMENDED SHEET
~1 72959 - 2~ - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration shaking ~h~k;ng in diesel fuel 70 F9 R9 strongly weakly strongly 5 ppm red yellow yellow 71 F9 R10 strongly almost strongly 5 ppm red colorless yellow 72 F10 Rl strongly almost strongly 20 ppm orange colorless yellow 73 F10 R2 strongly almo~t strongly 20 ppm orange colorless yellow 74 F10 R3 strongly almost strongly 20 ppm orange colorless yellow 75 F10 R8 strongly weakly strongly 20 ppm orange yellow yellow 76 F10 R9 weakly weakly B trongly 20 ppm yellow yellow yellow 77 F10 R10 strongly slightly strongly 20 ppm orange yellow yellow 78 Fll R1 orange weakly yellow 5 ppm yellow 79 Fll R2 strongly weakly strongly 5 ppm orange orange yellow 80 Fll R3 strongly almost strongly 5 ppm orange colorless yellow 81 Fll R4 strongly almost strongly 5 ppm red colorless yellow 30 82 Fll R5 strongly weakly strongly 5 ppm orange orange yellow 83 Fll R6 strongly weakly strongly 5 ppm orange orange yellow 84 Fll R7 strongly weakly strongly 5 ppm orange orange yellow 85 Fll R8 orange weakly strongly 5 ppm orange yellow AMENDED SHEET
21 1~9~9 - 22 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~k;ng shaking in diesel fuel 86 F11 R9 strongly weakly strongly 10 ppm bright yellow yellow red 87 F11 R10 strongly weakly strongly 10 ppm red yellow yellow 88 F12 R1 strongly almost strongly 5 ppm violet colorless yellow 89 F12 R2 strongly almost strongly 5 ppm violet colorless yellow 1590 F12 R3 strongly almost strongly 5 ppm dark blue colorless yellow 91 F12 R4 strongly weakly strongly 5 ppm green green yellow 92 F12 R5 strongly weakly strongly 5 ppm violet red yellow 93 F12 R6 strongly almost strongly 5 ppm violet colorless yellow 94 F12 R7 strongly almost strongly 5 ppm bluish colorless yellow gray 95 F12 R8 strongly almost strongly 5 ppm reddish colorless yellow violet 96 F12 R9 strongly weakly strongly 5 ppm red yellow yellow 97 F12 RlO strongly almost strongly 5 ppm violet colorless yellow 98 F13 Rl strongly almost strongly 5 ppm violet colorless yellow 3599 F13 R2 strongly weakly strongly 5 ppm yellowish yellow yellow orange 100 F13 R3 strongly almost strongly 5 ppm violet colorless yellow AMENDED SHEET
2~ 7~q~'9 - 23 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration BhA~;ng ~hAk;ng in diesel fuel 101 F13 R4 strongly weakly strongly 5 ppm orange yellow yellow 102 F13 R5 strongly weakly strongly 5 ppm orange yellow yellow 103 F13 R6 strongly weakly strongly 5 ppm orange yellow yellow 104 F13 R7 strongly weakly strongly 5 ppm orange yellow yellow 105 F13 R8 strongly weakly strongly 5 ppm orange yellow yellow 106 F13 R9 strongly weakly strongly 5 ppm red yellow yellow 107 F13 R10 strongly weakly strongly 5 ppm dark red yellow yellow 108 Fl4 R1 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 109 F14 R2 strongly almost strongly 5 ppm violet colorless yellow 110 F14 R3 strongly almost strongly 5 ppm ~iolet colorless yellow 111 Fl4 R4 strongly almost strongly 5 ppm green colorless yellow 112 F14 R5 strongly almost strongly 5 ppm reddish colorless yellow violet 113 F14 R6 strongly almost strongly 5 ppm dark blue colorless yellow 114 F14 R7 strongly almost strongly 5 ppm reddish colorless yellow ~iolet 115 F14 R8 strongly almost strongly 5 ppm bright colorless yellow blue AMENDED SHEET
2 j /' ~ !9 ~ 9 - 24 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~king R~k;n~ in diesel fuel 116 F14 R9 strongly weakly Rtrongly 5 ppm bright yellow yellow blue 117 F14 R10 ~trongly weakly strongly 5 ppm violet yellow yellow 118 F15 R1 strongly weakly strongly 5 ppm yellowish yellow orange brown 119 F15 R2 strongly weakly strongly 5 ppm reddish yellow orange brown 120 F15 R3 strongly weakly strongly 5 ppm reddish yellow orange violet 121 F15 R4 strongly weakly strongly 5 ppm yellow yellow orange 122 F15 R5 strongly weakly strongly 5 ppm red yellow orange 123 F15 R6 strongly weakly strongly 5 ppm yellowish yellow orange green 124 F15 R7 yellowish weakly strongly 5 ppm brown yellow orange 125 F15 R8 greenish weakly strongly 5 ppm gray yellow orange 126 F15 R9 colorles~ weakly strongly 5 ppm yellowish orange orange 127 F15 R10 strongly weakly strongly 5 ppm reddish yellow orange brown 128 F16 R1 strongly weakly strongly 5 ppm orange yellow yellow 129 F16 R2 strongly weakly strongly 5 ppm orange yellow yellow AMENDED SHEET
;~ 7f~95'?
- 25 - O.Z. 0050/44380 Ex. Dye Re- Hue of Hue of Hue of Marker No. agent aqueous oily phase oily phase concen-phase after before tration ~h~k~ n~ shaking in diesel fuel 130 F16 R3 strongly weakly strongly 5 ppm orange yellow yellow 131 F16 R4 strongly weakly strongly 5 ppm yellow yellow yellow 132 F16 R5 strongly weakly strongly 5 ppm orange yellow yellow 133 F16 R6 strongly weakly strongly 5 ppm orange yellow yellow 134 F16 R7 strongly weakly strongly 5 ppm orange yellow yellow 135 F16 R8 strongly weakly strongly 5 ppm orange yellow yellow 136 F16 R9 strongly weakly strongly 5 ppm orange yellow yellow 137 F16 R10 strongly weakly strongly 5 ppm orange yellow yellow EXAMPLE 138 (Preparation of F9) a) 42.6 g (0.04 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 32 ml of water and 12 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 20 g of ice, 7 ml of toluene and 12 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 3.76 g (0.04 mol) of phenol and 100 ml of water were adjusted with 50% strength by weight sodium hydrox-ide solution to pH 6.4 and admixed at 0C with the diazonium salt solution described under a). The pH
was held between 4 and 5 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH was reduced to 1.5 with 10% strength by AMENDED SHEET
- 26 - O.Z. 0050/44380 weight hydrochloric acid and the precipitated solid was isolated.
Yield: 10.1 g EXANPLE 139 (Preparation of Fll) a) 3.0 g (0.02 mol) of methyl anthranilate were dis-solved at 0C in 30 ml of water, 50 g of ice and 5 ml of concentrated hydrochloric acid and then admixed with 6 ml of 23% strength by weight aqueous sodium nitrite solution. The mixture was then stirred at from 0 to 5C for 30 minutes until a clear solution had formed.
b) 2.7 g (0.02 mol) of 2,3,6-trimethylphenol in 100 ml of water were adjusted with 50% strength by weight sodium hydroxide solution to pH 13 and admixed with the diazonium salt solution described under a).
After stirring overnight the pH was reduced to 2.1 with 10% strength by weight hydrochloric acid and the precipitated solid was isolated.
Yield: 5.8 g EXAMPLE 140 (Preparation of F14) a) 7.19 g (0.05 mol) of p-nitroaniline and 0.1 g of a wetting agent were suspended in 45 ml of water and 17.5 ml of 30% strength by weight hydrochloric acid.
The suspension was then a~;Ye~ with 55 g of ice and 16.5 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 0 to 5C for 1 h.
b) 7.56 g (0.05 mol) of 2-monoethylamino-4-methylphenol were added to 100 ml of water and adjusted with 50%
strength by weight sodium hydroxide solution to pH
10. Then the diazonium salt solution described under a) was added at 5C. The pH was held between 7 and 8 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH dropped to 4.6 and the precipitated solid was filtered off with suction.
~1~ NV~V SHEET
q~
- 27 - O.Z. 0050/44380 Yield: 14.1 g EXAMPLE 141 (Preparation of F15) a) 53.3 g (0.05 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 40 ml of water and 15 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 25 g of ice, 8.4 ml of toluene and 15 ml of 23% strength by weight aqueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 7.56 g (0.05 mol) of 2-monoethylamino-4-methylphenol were added to 100 ml of water and pH 10 was set with 50% strength by weight sodium hydroxide solution.
Then the diazonium salt solution described under a) was added at 5C. The pH was held between 7 and 8 with 10% strength by weight sodium hydroxide solution. After stirring overnight the pH was adjus-ted with hydrochloric acid to 1.5 and the precip-itated solid was filtered off with suction.
Yield: 15.9 g EXANPLE 142 (Preparation of F16) a) 42.6 g (0.04 mol) of m-aminoazotoluene hydrochloride (24.5% strength by weight) and 0.2 g of a wetting agent were suspended in 32 ml of water and 12 ml of 30% strength by weight hydrochloric acid. The sus-pension was then admixed with 20 g of ice, 7 ml of toluene and 12 ml of 23% strength by weight a~ueous sodium nitrite solution and stirred at from 5 to 10C for 2 h.
b) 6.7 g (0.04 mol) of m-N,N-diethylaminophenol were added to 100 ml of water and pH 13.2 was set with 50% strength by weight sodium hydroxide solution.
Then the diazonium salt solution described under a) was added at 5C. The pH was held between 4 and 5 with 10% strength by weight sodium hydroxide 801-ution. After stirring overnight the pH was reduced AMENDED SHEET
- ~8 - O.Z. 0050/44380 to 1.5 with 10% ~trength by weight hydrochloric acid and the precipitated solid was isolated.
Yield: 16 g The same method gives the dyes F12 and F13.
AMENDED SHEET
Claims (7)
1. A method for detecting azo dye marked mineral oils by treating the marked mineral oil with an extrac-tant comprising water, a solvent and a base, the azo dye transferring from the mineral oil into the aqueous phase, which comprises using as marker an azo dye of the formula Ia (Ia), where m is from 1 to 4, X1 is hydrogen, cyano, nitro or phenylazo which may be monosubstituted or disubstituted by C1-C4-alkyl, X2 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C13-alkoxycarbonyl, X3 is hydrogen or C1-C4-alkyl, and X4 is hydrogen or C1-C8-alkyl, which may be phenyl-substituted, or of the formula Ib (Ib) where X1 is hydrogen, or C1-C4-alkyl-substituted phenylazo, X2 is hydrogen, X3 is hydrogen or C1-C4-alkyl, X4 is hydrogen, C1-C4-alkyl, C1-C4-dialkylamino or C1-C16-monoalkylamino, X5 is hydrogen or C1-C4-alkyl, and X6 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy, with the proviso that a) at least one of the three radicals X1, X2 and X3 is different from hydrogen, b) X2 may also be cyano when X4 is C1-C4-dialkylamino, c) X2 may also be C1-C4-alkoxycarbonyl when all the radicals X4, X5 and X6 are different from hydrogen, and d) one of the radicals X1, X2 or X3 may also be nitro when X4 is C1-C16-monoalkylamino and X6 is C1-C4-alkyl, as solvent a partially or completely water-miscible organic solvent, and as base an alkali or alkaline earth metal hydroxide, an alkali metal carbonate or an ammonium compound of the formula II
(II), where R1, R2, R3 and R4 are each independently of the others C1-C16-alkyl or benzyl.
(II), where R1, R2, R3 and R4 are each independently of the others C1-C16-alkyl or benzyl.
2. A method as claimed in claim 1, wherein the base used is an alkali or alkaline earth metal hydroxide.
3. The use of azo dyes of the formula Ia (Ia) where m is from 1 to 4, X1 is hydrogen, cyano, nitro or phenylazo which may be monosubstituted or disubstituted by C1-C4-alkyl, X2 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C13-alkoxycarbonyl, X3 is hydrogen or C1-C4-alkyl, and X4 is hydrogen or C1-C4-alkyl, which may be phenyl-substituted, for marking mineral oils.
4. A use as claimed in claim 3 of azo dyes where X4 is hydrogen or 1-phenylethyl.
5. A use as claimed in claim 3 of azo dyes where X1 is hydrogen or methyl-monosubstituted phenylazo, X2 is methyl or C1-C13-alkoxycarbonyl, and X3 is hydrogen or methyl.
6. A use as claimed in claim 3 of azo dyes, conform-ing to the formula Ic (Ic) where Y is C7-C11-alkyl-
7. The use for marking mineral oils of azo dyes of the formula Ib (Ib), where X1 is hydrogen, or C1-C4-alkyl-substituted phenylazo, X2 is hydrogen, X3 is hydrogen or C1-C4-alkyl, X4 is hydrogen, C1-C4-alkyl, C1-C4-dialkylamino or C1-C16-monoalkylamino, X5 is hydrogen or C1-C4-alkyl, and X6 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy, with the proviso that a) at least one of the three radicals X1, X2 and X3 is different from hydrogen, b) X2 may also be cyano when X4 is C1-C4-dialkylamino, c) X2 may also be C1-C4-alkoxycarbonyl when all the radicals X4, X5 and X6 are different from hydrogen, and d) one of the radicals X1, X2 or X3 may also be nitro when X4 is C1-C16-monoalkylamino and X6 is C1-C4-alkyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4334678A DE4334678A1 (en) | 1993-10-12 | 1993-10-12 | Method for the detection of labeled mineral oils and new azo dyes |
| DEP4334678.2 | 1993-10-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2172959A1 true CA2172959A1 (en) | 1995-04-20 |
Family
ID=6499917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002172959A Abandoned CA2172959A1 (en) | 1993-10-12 | 1994-09-30 | Process for detecting marked mineral oils and new azo dyes |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US5487770A (en) |
| EP (1) | EP0723574B1 (en) |
| JP (1) | JPH09504314A (en) |
| KR (1) | KR100300774B1 (en) |
| CN (1) | CN1046756C (en) |
| AT (1) | ATE180823T1 (en) |
| AU (1) | AU682540B2 (en) |
| BR (1) | BR9407810A (en) |
| CA (1) | CA2172959A1 (en) |
| CZ (1) | CZ9601018A3 (en) |
| DE (2) | DE4334678A1 (en) |
| DK (1) | DK0723574T3 (en) |
| ES (1) | ES2134357T3 (en) |
| FI (1) | FI961602A0 (en) |
| GR (1) | GR3030494T3 (en) |
| HU (1) | HU217768B (en) |
| MX (1) | MX193901B (en) |
| NO (1) | NO961434L (en) |
| PH (1) | PH32006A (en) |
| PL (1) | PL313967A1 (en) |
| TW (1) | TW291494B (en) |
| WO (1) | WO1995010581A1 (en) |
| ZA (1) | ZA947908B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX9707881A (en) * | 1995-04-13 | 1998-03-31 | United Color Mfg Inc | Developer system for base reactable petroleum fuel markers. |
| DE69614843T2 (en) * | 1995-04-13 | 2002-04-11 | United Color Mfg Inc | COLORLESS PETROLEUM MARKING AGENT |
| US5737871A (en) * | 1996-04-26 | 1998-04-14 | Morton International, Inc. | Method of preparing and utilizing petroleum fuel markers |
| FR2787577B1 (en) * | 1998-12-16 | 2001-03-02 | Total Raffinage Distrib | COLORED INDICATOR FOR MEASURING THE DISTRIBUTION OF HYDROCARBON FAMILIES CONTAINED IN A MIXTURE, METHOD FOR OBTAINING SAME AND USES THEREOF |
| US6482651B1 (en) | 1999-06-30 | 2002-11-19 | United Color Manufacturing, Inc. | Aromatic esters for marking or tagging petroleum products |
| DK1642885T3 (en) * | 2000-08-29 | 2010-01-04 | Biocon Ltd | Use of a pharmaceutical composition containing a para-aminophenyl acetic acid derivative for the treatment of inflammatory conditions of the gastrointestinal tract |
| US6514917B1 (en) * | 2001-08-28 | 2003-02-04 | United Color Manufacturing, Inc. | Molecular tags for organic solvent systems |
| US8048924B2 (en) * | 2001-08-29 | 2011-11-01 | Biocon Limited | Methods and compositions employing 4-aminophenylacetic acid compounds |
| GB0222728D0 (en) * | 2002-10-01 | 2002-11-06 | Shell Int Research | System for identifying lubricating oils |
| GB0406770D0 (en) * | 2004-03-25 | 2004-04-28 | Customs & Excise | Hydrocarbon markers |
| EP1773767B1 (en) | 2004-07-07 | 2016-03-09 | Biocon Limited | Synthesis of azo bonded immunoregulatory compounds |
| JP2009516162A (en) * | 2005-11-11 | 2009-04-16 | モレキュラー・ビジョン・リミテッド | Microfluidic device |
| US8257975B2 (en) * | 2008-03-25 | 2012-09-04 | The Lubrizol Corporation | Marker dyes for petroleum products |
| CN106893356A (en) * | 2017-01-10 | 2017-06-27 | 泉州市希姆色彩研究院有限公司 | A kind of disperse orange dye of water fastness high and preparation method thereof |
| WO2022161960A1 (en) | 2021-01-29 | 2022-08-04 | Basf Se | A method of marking fuels |
| EP4327073A1 (en) | 2021-04-20 | 2024-02-28 | Basf Se | A method of detecting one or more markers in a petroleum fuel using a photoacoustic detector |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2925333A (en) * | 1955-05-24 | 1960-02-16 | Eastman Kodak Co | Colored hydrocarbons |
| GB905321A (en) * | 1959-04-16 | 1962-09-05 | Acna | Bis-azo dyes |
| US3056642A (en) * | 1959-12-22 | 1962-10-02 | American Cyanamid Co | Granular form red oil soluble dye |
| US3704106A (en) * | 1967-10-24 | 1972-11-28 | Morton Int Inc | Colored petroleum distillate |
| US3690809A (en) * | 1971-04-05 | 1972-09-12 | Morton Int Inc | Liquid azo dye composition and process therefor |
| US3764273A (en) * | 1971-06-14 | 1973-10-09 | Morton Norwich Products Inc | Novel marker for water immiscible organic liquids and method of marking same |
| DE2157609C3 (en) * | 1971-11-20 | 1974-09-12 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Oil-soluble monoazo dye mixtures, process for their preparation and their use |
| JPS6027695B2 (en) * | 1977-03-15 | 1985-07-01 | バイエル・アクチエンゲゼルシヤフト | Azo compound |
| DE2852863A1 (en) * | 1978-12-07 | 1980-06-19 | Basf Ag | COMPOUNDS SOLUBLE IN ORGANIC SOLVENTS |
| DE2952759A1 (en) * | 1979-12-29 | 1981-07-09 | Basf Ag, 6700 Ludwigshafen | SOLUBLE DYES |
| DE3401881A1 (en) * | 1984-01-20 | 1985-09-26 | Cassella Ag, 6000 Frankfurt | BISAZO DYES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3627461A1 (en) * | 1986-08-13 | 1988-02-25 | Basf Ag | DYE MIXTURES |
| US5156653A (en) * | 1991-04-18 | 1992-10-20 | Morton International, Inc. | Silent markers for petroleum, method of tagging, and method of detection |
| US5252106A (en) * | 1992-07-29 | 1993-10-12 | Morton International, Inc. | Base extractable petroleum markers |
-
1993
- 1993-10-12 DE DE4334678A patent/DE4334678A1/en not_active Withdrawn
-
1994
- 1994-09-29 PH PH49090A patent/PH32006A/en unknown
- 1994-09-30 AU AU77842/94A patent/AU682540B2/en not_active Ceased
- 1994-09-30 KR KR1019960701889A patent/KR100300774B1/en not_active IP Right Cessation
- 1994-09-30 ES ES94928400T patent/ES2134357T3/en not_active Expired - Lifetime
- 1994-09-30 CA CA002172959A patent/CA2172959A1/en not_active Abandoned
- 1994-09-30 AT AT94928400T patent/ATE180823T1/en not_active IP Right Cessation
- 1994-09-30 BR BR9407810A patent/BR9407810A/en not_active IP Right Cessation
- 1994-09-30 PL PL94313967A patent/PL313967A1/en unknown
- 1994-09-30 EP EP94928400A patent/EP0723574B1/en not_active Expired - Lifetime
- 1994-09-30 CN CN94194282A patent/CN1046756C/en not_active Expired - Fee Related
- 1994-09-30 CZ CZ19961018A patent/CZ9601018A3/en unknown
- 1994-09-30 DK DK94928400T patent/DK0723574T3/en active
- 1994-09-30 DE DE59408367T patent/DE59408367D1/en not_active Expired - Lifetime
- 1994-09-30 JP JP7511234A patent/JPH09504314A/en active Pending
- 1994-09-30 HU HU9600946A patent/HU217768B/en not_active IP Right Cessation
- 1994-09-30 WO PCT/EP1994/003259 patent/WO1995010581A1/en not_active Application Discontinuation
- 1994-10-04 MX MX9407695A patent/MX193901B/es not_active IP Right Cessation
- 1994-10-05 TW TW83109234A patent/TW291494B/zh active
- 1994-10-11 ZA ZA947908A patent/ZA947908B/en unknown
- 1994-10-12 US US08/321,629 patent/US5487770A/en not_active Expired - Fee Related
-
1996
- 1996-04-11 NO NO961434A patent/NO961434L/en not_active Application Discontinuation
- 1996-04-11 FI FI961602A patent/FI961602A0/en unknown
-
1999
- 1999-06-10 GR GR990401569T patent/GR3030494T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046756C (en) | 1999-11-24 |
| KR100300774B1 (en) | 2001-11-22 |
| FI961602A (en) | 1996-04-11 |
| NO961434D0 (en) | 1996-04-11 |
| JPH09504314A (en) | 1997-04-28 |
| KR960705003A (en) | 1996-10-09 |
| CZ9601018A3 (en) | 2002-01-16 |
| HUT74124A (en) | 1996-11-28 |
| PL313967A1 (en) | 1996-08-05 |
| EP0723574B1 (en) | 1999-06-02 |
| US5487770A (en) | 1996-01-30 |
| PH32006A (en) | 1999-06-02 |
| EP0723574A1 (en) | 1996-07-31 |
| ES2134357T3 (en) | 1999-10-01 |
| NO961434L (en) | 1996-04-11 |
| CN1141055A (en) | 1997-01-22 |
| GR3030494T3 (en) | 1999-10-29 |
| DK0723574T3 (en) | 1999-11-15 |
| TW291494B (en) | 1996-11-21 |
| ATE180823T1 (en) | 1999-06-15 |
| WO1995010581A1 (en) | 1995-04-20 |
| HU217768B (en) | 2000-04-28 |
| BR9407810A (en) | 1997-05-06 |
| DE4334678A1 (en) | 1995-04-13 |
| AU7784294A (en) | 1995-05-04 |
| ZA947908B (en) | 1996-04-11 |
| DE59408367D1 (en) | 1999-07-08 |
| AU682540B2 (en) | 1997-10-09 |
| MX193901B (en) | 1999-11-01 |
| FI961602A0 (en) | 1996-04-11 |
| HU9600946D0 (en) | 1996-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2172959A1 (en) | Process for detecting marked mineral oils and new azo dyes | |
| US5627077A (en) | Anilines as markers for mineral oils | |
| CA1128513A (en) | Marker for petroleum fuels | |
| EP0509818B1 (en) | Silent markers for petroleum, method of tagging, and method of detection | |
| RU2298580C2 (en) | Hydrocarbon marking method | |
| KR100854158B1 (en) | A composition of a petroleum product with marker, a marker, and a method for identification of a petroleum product | |
| US5252106A (en) | Base extractable petroleum markers | |
| CA2026130C (en) | Aniline-based oil-soluble azo dyes | |
| AU691219B2 (en) | Use of azo dyes for marking hydrocarbons and novel azo dyes | |
| US5490872A (en) | Acid extractable petroleum fuel markers | |
| JPH04320455A (en) | Azo dye | |
| US5663386A (en) | Method for marking mineral oils with amthraquinones | |
| HUT73873A (en) | Method of detecting naphthylamines in mineral oils | |
| US6083285A (en) | N,N-dialkylaniline azo dye solutions | |
| GB2354070A (en) | Markers for identifying liquids | |
| RU2100411C1 (en) | Method for marking mineral oil and method for detecting marker | |
| MXPA97000116A (en) | Use of leukotriarilmetans for the marking of hydrocarb |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |